US4376720A - Olefin polymerization catalyst and olefin polymerization method using such catalyst - Google Patents
Olefin polymerization catalyst and olefin polymerization method using such catalyst Download PDFInfo
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- US4376720A US4376720A US06/211,991 US21199180A US4376720A US 4376720 A US4376720 A US 4376720A US 21199180 A US21199180 A US 21199180A US 4376720 A US4376720 A US 4376720A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 title claims description 49
- 239000002685 polymerization catalyst Substances 0.000 title abstract description 5
- 238000000034 method Methods 0.000 title description 15
- 125000002734 organomagnesium group Chemical group 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 15
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000004429 atom Chemical group 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229940117975 chromium trioxide Drugs 0.000 claims description 5
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 37
- 230000000694 effects Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000000071 blow moulding Methods 0.000 abstract description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 18
- 239000011651 chromium Substances 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 5
- 229910052751 metal Chemical group 0.000 description 5
- 239000002184 metal Chemical group 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 150000002901 organomagnesium compounds Chemical class 0.000 description 5
- -1 oxyhalides Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- CYHOFESITORDDD-UHFFFAOYSA-M C(CCC)O[Cr](=O)(=O)O Chemical group C(CCC)O[Cr](=O)(=O)O CYHOFESITORDDD-UHFFFAOYSA-M 0.000 description 1
- BCEIUDAMUFAQMG-UHFFFAOYSA-M CC(C)(C)O[Cr](O)(=O)=O Chemical compound CC(C)(C)O[Cr](O)(=O)=O BCEIUDAMUFAQMG-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910015243 LiMg Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- IXLQOOXAQLYREP-UHFFFAOYSA-K chromium(3+) 3-oxobutanoate Chemical compound [Cr+3].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O IXLQOOXAQLYREP-UHFFFAOYSA-K 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- AHXGRMIPHCAXFP-UHFFFAOYSA-L chromyl dichloride Chemical compound Cl[Cr](Cl)(=O)=O AHXGRMIPHCAXFP-UHFFFAOYSA-L 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004796 dialkyl magnesium compounds Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Definitions
- This invention relates to an olefin polymerization catalyst used for the polymerization of olefins, particularly ethylene or ethylene and other ⁇ -olefins, and an olefin polymerization method using such catalyst. More particularly, the invention relates to a novel and high-activity olefin polymerization catalyst composed of a combination of a solid component comprising a chromium compound supported by an inorganic oxide and a component containing a specific organomagnesium compound.
- the ethylene polymerization catalysts obtained by calcining the chromium compounds such as chromium oxide supported by an inorganic oxide carrier such as silica, silica-alumina, etc., are widely known as "Phillips catalysts".
- both the catalytic activity and the average molecular weight of the produced polymer greatly depend on the polymerization temperature, and in order to produce the polymers having a commercially required range of molecular weight, or of the order of tens of thousands to hundreds of thousands, while maintaining a sufficiently high catalyst activity, it was generally necessary to keep the polymerization temperature within the range of 100° to 200° C.
- the polymerization is carried out in such temperature range, the produced polymer stays dissolved in the reaction solvent, so that the viscosity of the reaction system rises excessively, giving rise to various problems such as increased difficulty in recovering the polymerization product, and thus it was hardly possible to elevate the produced polymer concentration to higher than 20%.
- a catalyst prepared by combining a chromium compound supported by a carrier such as silica and a specific organomagnesium compound shows an extremely high catalytic activity in the polymerization not only at a temperature above 100° C. but also at a low temperature below 100° C. and also allows easy production of a polymer having a molecular weight suited for blow molding as well as a wide molecular weight distribution, and this finding has led to the attainment of this invention.
- the present invention provides a catalyst for olefin polymerization comprising:
- the catalyst of this invention comprising a combination of a carrier-supported chromium compound (solid component) and a specific organomagnesium compound is surprisingly improved in its catalytic activity; this catalyst is several times as high in catalytic activity as the known combination catalysts comprising an organoaluminum compound in combination with other compounds such as mentioned below.
- the catalyst of this invention comprising an organomagnesium complex compound containing the siloxy radicals and metal atoms M (such as aluminum) allows production of the polymers having a high melt index which indicates an average molecular weight convenient for molding works.
- Such polymers also have a wide molecular weight distribution suited for blow molding. Further, the hydrocarbon solutions of the siloxy-containing organomagnesium complex compounds according to this invention show a far higher activity than the ether solutions of the so-called Grignard compounds.
- the inorganic oxide carrier used in this invention there may be employed a variety of substances such as silica, alumina, silica-alumina, thoria, zirconia, etc., but among them, silica and silica-alumina are most preferred. No specific restriction is however placed on these substances and any commercially available high-activity silica catalyst (highly porous and having a large surface area) may be used.
- the chromium compound to be supported by said carrier there may be cited the oxides of chromium and the compounds which form at least partially chromium oxide when calcined, such as halides, oxyhalides, nitrates, sulfates, oxalates, alcoholates, etc. More definitely, one may cite chromium trioxide, chromyl chloride, potassium dichromate, ammonium chromate, chromium nitrate, chromium acetylacetate, ditertiary butyl chromate, etc. Chromium trioxide is most preferred.
- Supporting of a chromium compound by a carrier can be accomplished by a known means such as impregnation, distilling-off of the solvent or adhesion by sublimation.
- the amount of chromium to be supported is within the range of 0.05 to 5%, preferably 0.1 to 3%, in terms of weight percent of the chromium atoms to the weight of the carrier.
- Activation by calcination can be also attained by a known method. It is usually performed in a nonreducing atmosphere, for example in the presence of oxygen, but it is also possible to accomplish such calcination in the presence of an inert gas or under reduced pressure. It is desirable to use air which is substantially free of moisture. Such calcination is carried out at a temperature above 300° C., preferably a temperature of from 400° C. to 900° C., for a period of several minutes to several ten hours, preferably 30 minutes to 10 hours. It is recommended to perform said calcination activation under a fluidized condition in a stream of dry air at a required rate.
- the catalyst system of this invention may comprise a solid component obtained by first calcining a carrier such as silica and then supporting thereon a chromium compound soluble in the non-aqueous solvents, such as t-butyl chromate, in a per se known way.
- M is an atom selected from aluminum, zinc, boron, beryllium and lithium, preferably aluminum or zinc, most preferably aluminum.
- R 1 , R 2 and R 3 represent respectively a hydrocarbon radical such as an alkyl group, a cycloalkyl group or an aryl group, preferably one having 1 to 20 carbon atoms.
- An alkyl group is preferably used.
- the ratio of Mg to M ( ⁇ / ⁇ ), which is an important factor in this invention, is preferably not smaller than 0.5, more preferably not smaller than 1.
- X and Y represent a polar group. More definitely, X is a siloxy group of the general formula: OSiR.sup.
- R 5 R 6 R 7 and Y is an alkoxy group of the general formula: OR 4 , a siloxy group of the general formula: OSiR 5 R 6 R 7 , an amino group of the general formula: NR 8 R 9 or a sulfide group of the general formula: SR 10 .
- Y is preferred to be an alkoxy group or a siloxy group.
- R 5 to R 9 represent respectively hydrogen atom or a hydrocarbon radical which preferably has 1 to 15 carbon atoms
- R 4 and R 10 represent a hydrocarbon radical having preferably 1 to 15 carbon atoms.
- the ratio of the polar group to the metal atoms (s+t)/( ⁇ + ⁇ ) is also an important consideration; it is preferably not greater than 1, most preferably not greater than 0.8.
- the ratio of the siloxy group to the metal atoms (s/( ⁇ + ⁇ )) is not smaller than 0.2 but not greater than 1.5, preferably not greater than 1.0, more preferably not greater than 0.8. Fulfillment of said requirements on M and siloxy group (OSiR 5 R 6 R 7 ) leads to the typical effect of this invention, particularly a satisfactory result in melt index, as shown in Examples 1-7 and Comparative Examples C and D.
- Said organomagnesium complex compounds soluble in the inert hydrocarbons can be synthesized according to the methods shown in the already published applications by this applicant (for example, see U.S. Pat. Nos. 4,027,089, 4,146,549 and 3,989,878).
- the inert hydrocarbon medium one may favorably use an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as benzene or toluene, or an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane.
- Said both solid catalyst component and organomagnesium component may be added in the polymerization system under the prescribed polymerization conditions, or they may be combined prior to the polymerization.
- the solid catalyst component may be first treated with said organomagnesium component, then further combined with an organomagnesium compound and introduced into the polymerization system.
- the ratio between said both components to be combined is recommended to be within the range of 0.01-3,000, preferably 0.1-100.
- the olefins that can be polymerized by using the catalyst of this invention are ⁇ -olefins, particularly ethylene, but the catalyst of this invention can be also used for the copolymerization of ethylene and a monoolefin such as propylene, butene-1, hexene-1, etc., or for the polymerization in the presence of a diene such as butadiene, isoprene, etc.
- Copolymerization by use of the catalyst of this invention allows preparation of the polymers having a density within the range of 0.91 to 0.97 g/cm 3 .
- the catalyst is introduced into the reactor together with a polymerization solvent, for example an aliphatic hydrocarbon such as propane, butane, pentane, hexane or heptane, an aromatic hydrocarbon such as benzene, toluene or xylene or an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, and the polymerization may be carried out at a temperature ranging from room temperature to 320° C. in an inert atmosphere by charging ethylene under a pressure of 1 to 200 kg/cm 2 .
- a polymerization solvent for example an aliphatic hydrocarbon such as propane, butane, pentane, hexane or heptane, an aromatic hydrocarbon such as benzene, toluene or xylene or an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane
- vapor phase polymerization can be accomplished by employing a fluidized bed or moving bed system so as to provide good contact between ethylene and catalyst, or by adopting a proper measure such as effecting mixing by stirring, at a temperature of from room temperature to 120° C. by charging ethylene under a pressure of 1 to 50 kg/cm 2 .
- the catalyst of this invention features its high performance; it shows a high activity even under the relatively low-temperature and low-pressure conditions of around 80° C. and around 10 kg/cm 2 .
- the rise of viscosity of the polymerization system is very limited. It is therefore possible to increase the polymer concentration in the polymerization system to higher than 30%, resulting in many advantages such as improved production efficiency.
- the high activity of the catalyst it is possible to dispense with the step of removing the catalyst residue from the produced polymer.
- the polymerization may be of an ordinary one-stage polymerization system using one reaction zone or may be of a multi-stage polymerization system using a plurality of reaction zones.
- the polymers produced by using the catalyst of this invention even when using an ordinary one-stage polymerization system, have a wide molecular weight distribution and are also relatively high in molecular weight, so that they can be favorably used for blow molding or film molding.
- the polymerization is carried out under two or more different reaction conditions, there can be produced the polymers having an even wider molecular weight distribution.
- catalytic activity used in the following Examples signifies the amount (g) of the polymer produced per one gram of chromium in the solid catalyst per one hour of the polymerization under the monomer pressure of 10 kg/cm 2 .
- M.I stands for the melt index measured according to ASTM D-1238 at a temperature of 190° C. under a load of 2.16 kg.
- F.R is the quotient given by dividing the value of high-load melt index measured at 190° C. under the load of 21.6 kg by the above-defined M.I. This F.R. is known to the artisans as an index for indicating the broadness of molecular weight distribution.
- Example 1 The process of Example 1 was repeated but by using 0.1 mmol of triethylaluminum instead of 0.1 mmol of the organomagnesium complex.
- the results of the polymerization were as follows. Polymer yield: 60 g; catalytic activity: 150,000 g-polymer/g-Cr/hr; M.I.: 0.25; F.R.: 140.
- Example 1 The process of Example 1 was repeated but by using 0.1 mmol of n-butylmagnesium chloride (di-n-butyl ether solution) instead of 0.1 mmol of the organomagnesium complex (heptane solution), obtaining the following results.
- Example 1 The process of Example 1 was repeated but by using 0.1 mmol of a dialkylmagnesium complex (heptane solution) having the composition of AlMg 6 (n--C 4 H 9 ) 12 (C 2 H 5 ) 3 instead of 0.1 mmol of the siloxy radical-containing organomagnesium complex (heptane solution) to obtain the following results.
- Example 1 The process of Example 1 was repeated but by using 0.1 mmol of dibutylmagnesium having the composition of (sec-C 4 H 9 )Mg(n--C 4 H 9 ) (heptane solution, produced by Lithium Corporation of America) instead of 0.1 mmol of the siloxy radical-containing organomagnesium complex (heptane solution).
- the polymerization gave the following results. Polymer yield: 208 g; catalytic activity: 520,000 g-polymer/g-Cr/hr; M.I.: lower than 0.01.
- Example 1 The polymerization of Example 1 was carried out by changing the organomagnesium component and its amount to obtain the results shown in Table 1 below.
- siloxy-containing organomagnesium complex solution having the composition of AlMg 4 (C 2 H 5 ) 1 .64 (n--C 4 H 9 ) 4 .36 (OSi.H.CH 3 .C 2 H 5 ) 1 .36 (OSi.H.CH 3 .n--C 4 H 9 ) 3 .64.
- Polymerization was carried out in the same way as Example 1 by using said siloxy-containing organomagnesium complex solution as the organomagnesium component, obtaining the following results.
- Example 1 The polymerization of Example 1 was carried out by changing the organomagnesium component and its amount, obtaining the results shown in Table 2.
- the alkoxy group was introduced by reacting a corresponding alcohol with the organometallic compounds.
- the catalyst synthesis and polymerization were performed in the same way as Example 1 except that 1.6 g of chromium nitrate nonahydrate was used instead of 0.4 g of chromium trioxide in the synthesis of the solid component (a).
- the results of the polymerization were as follows. Polymer yield: 236 g; catalytic activity: 590,000 g-polymer/g-Cr/hr; M.I.: 0.29.
- Example 1 The polymerization of Example 1 was carried out but by using an ethylene and butene-1 mixed gas (containing 15 mol% of butene-1) instead of ethylene, and isobutane as polymerization solvent instead of hexane, at a temperature of 80° C. under mixed gas partial pressure of 10 kg/cm 2 , hydrogen partial pressure of 1 kg/cm 2 and overall pressure (including solvent vapor pressure) of 23 kg/cm 2 and by using the catalyst of Example 1. There were obtained the following results of polymerization. Polymer yield: 216 g; catalytic activity: 540,000 g-polymer/g-Cr/hr; M.I.: 0.63; polymer density: 0.924.
- an ethylene and butene-1 mixed gas containing 15 mol% of butene-1
- isobutane as polymerization solvent instead of hexane
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Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP15634779A JPS595602B2 (ja) | 1979-12-04 | 1979-12-04 | オレフインの重合用触媒 |
JP54-156347 | 1979-12-04 | ||
JP55-33364 | 1980-03-18 | ||
JP3336480A JPS595604B2 (ja) | 1980-03-18 | 1980-03-18 | 斜板式アキシャルプランジャ型油圧作動装置 |
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US4376720A true US4376720A (en) | 1983-03-15 |
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Application Number | Title | Priority Date | Filing Date |
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US06/211,991 Expired - Lifetime US4376720A (en) | 1979-12-04 | 1980-12-01 | Olefin polymerization catalyst and olefin polymerization method using such catalyst |
Country Status (6)
Country | Link |
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US (1) | US4376720A (fr) |
EP (1) | EP0030438B1 (fr) |
BR (1) | BR8007883A (fr) |
CA (1) | CA1144914A (fr) |
DE (1) | DE3068466D1 (fr) |
MX (1) | MX156899A (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US5010151A (en) * | 1986-12-10 | 1991-04-23 | Idemitsu Petrochemical Co., Ltd. | Method for preparing ethylene polymers |
Families Citing this family (1)
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US4816432A (en) * | 1987-05-28 | 1989-03-28 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha olefins |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2023153A (en) * | 1934-07-21 | 1935-12-03 | Marino De Lorenzo | Fluid operated valve for fermentation receptacles |
US3989878A (en) * | 1974-05-25 | 1976-11-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Catalyst and process of production of polyethylene |
US4027089A (en) * | 1974-05-25 | 1977-05-31 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for polymerizing ethylene |
US4146695A (en) * | 1976-05-24 | 1979-03-27 | Stamicarbon, B.V. | Chromium-based catalysts for the polymerization of 1-alkenes |
GB2023153A (en) | 1978-06-13 | 1979-12-28 | Bp Chem Int Ltd | Polymerisation of ethylene |
Family Cites Families (2)
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LU34020A1 (fr) * | 1953-01-27 | 1956-02-06 | ||
NL278927A (fr) * | 1962-04-16 |
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1980
- 1980-11-27 CA CA000365597A patent/CA1144914A/fr not_active Expired
- 1980-12-01 US US06/211,991 patent/US4376720A/en not_active Expired - Lifetime
- 1980-12-01 DE DE8080304312T patent/DE3068466D1/de not_active Expired
- 1980-12-01 EP EP80304312A patent/EP0030438B1/fr not_active Expired
- 1980-12-02 BR BR8007883A patent/BR8007883A/pt unknown
- 1980-12-03 MX MX185020A patent/MX156899A/es unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2023153A (en) * | 1934-07-21 | 1935-12-03 | Marino De Lorenzo | Fluid operated valve for fermentation receptacles |
US3989878A (en) * | 1974-05-25 | 1976-11-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Catalyst and process of production of polyethylene |
US4027089A (en) * | 1974-05-25 | 1977-05-31 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for polymerizing ethylene |
US4146549A (en) * | 1974-05-25 | 1979-03-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Hydrocarbon-soluble organoaluminum-magnesium complex |
US4146695A (en) * | 1976-05-24 | 1979-03-27 | Stamicarbon, B.V. | Chromium-based catalysts for the polymerization of 1-alkenes |
GB2023153A (en) | 1978-06-13 | 1979-12-28 | Bp Chem Int Ltd | Polymerisation of ethylene |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5010151A (en) * | 1986-12-10 | 1991-04-23 | Idemitsu Petrochemical Co., Ltd. | Method for preparing ethylene polymers |
Also Published As
Publication number | Publication date |
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MX156899A (es) | 1988-10-13 |
EP0030438A1 (fr) | 1981-06-17 |
DE3068466D1 (en) | 1984-08-09 |
CA1144914A (fr) | 1983-04-19 |
BR8007883A (pt) | 1981-06-16 |
EP0030438B1 (fr) | 1984-07-04 |
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